HU203645B - Insecticidal and acaricidal compositions comprising 1-arylpzrayole derivative as active ingredient and process for producing the active ingredients - Google Patents

Description

The present invention relates to novel insecticidal and acaricidal compositions containing 1-arylpyrazole derivatives as active ingredients and to processes for their preparation.

Certain 1-arylpyrazole derivatives, such as 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- (N-methylamino) -4- (trifluoromethylthio), are known -) - Pyrazole or 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (dichlorofluoromethylthio) 5- (N-methylamino) pyrazole is a favorable insecticide have an effect (see European Patent Application Publication No. 0201852).

However, the effects of the compounds known in the art on the application of small amounts and low concentrations are not completely satisfactory against all insect pests and in all applications.

It has now been found that the novel 1-arylpyrazole derivatives of formula (I) wherein

R ¹ is hydrogen or C 1-4 alkyl,

R ^{2 is C} 1 -C 4 haloalkyl,

R ³ is hydrogen or C 1-4 alkyl,

R ⁴ is C 1 -C 4 alkyl or phenyl optionally substituted with halo, C 1 -C 4 alkyl or C 1 -C 4 alkoxy,

X is O or -N- (C 1 -C ₄ alkyl) m is 0 or 1 and n is 0.1 or 2 and

Ar is phenyl substituted with halogen, C 1-4 haloalkyl or C 1-4 haloalkoxy.

They show excellent insecticidal and acaricidal activity.

According to the present invention, the compounds of formula I (hereinafter referred to as "compounds of the invention") are prepared by:

a) for the preparation of compounds of formula (Ia) wherein R 1, R 2, R 3, R 4, Ar and n are as defined above, a 5-amino-1-arylpyrazole derivative of formula (I) wherein R 1, R 2, Ar and n are as defined above, reacted with an aldehyde or ketone of the general formula (ΠΙ), wherein R 3 and R 4 are as defined above, optionally in the presence of a diluent and optionally in the presence of a reaction facilitating agent; obsession

b) for preparing compounds of formula (Ib) where X ¹ is oxygen or N-alkyl group, and R ^1, R ^2, R ^3, R ^4, Ar and n are as defined above, - (II) 5amino formula a -1-arylpyrazole derivative wherein R ¹ , R ² , Ar and n are as defined above, with an orthoester or orthoic acid amide of formula IV, wherein R ^{5 is} C 1 -C ⁴ alkyl, and R ³ , R ⁴ and X ¹ is as defined above, optionally in the presence of a diluent and optionally in the presence of a reaction facilitating agent.

Surprisingly, the 1-arylpyrazole derivatives of the formula (I) according to the invention exhibit significantly better insecticidal activity than the 1-arylpyrazole derivatives known in the art, such as 1- [2,6-dichloro-4]. - (trifluoromethyl) phenyl] -5- (N-methylamino) -4- (trifluoromethylthio) pyrazole or 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] - 4- (dichlorofluoromethylthio) -5- (N-methylamino) pyrazole, i.e., known compounds which are similar in their chemical structure and activity to the compounds of the invention.

When starting materials are, for example, 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (trifluoromethylthio) pyrazole and benzaldehyde, process a) according to the invention is carried out in accordance with A). illustrate the reaction scheme.

For example, starting materials such as 5-amino-4- (dichlorofluoromethylthio) -1- [2-fluoro-6-chloro-4- (trifluoromethyl) phenyl] pyrazole and triethyl ortho-acetic acid are used. process b) according to the invention can be illustrated by the following reaction scheme B).

The 5-amino-1-arylpyrazole derivatives used as starting materials in the processes a) and b) according to the invention are defined in general terms by the general formula II. In the formula (II), R ¹ , R ² , Ar and n preferably represent the same groups as the preferred substituents for the formula (I) according to the invention.

The 5-amino-1-arylpyrazole derivatives of formula (Π) are known or may be prepared in a manner analogous to known processes (see European Patent Application 0201852).

The aldehydes and ketones which are useful as starting materials for carrying out the process (a) of the present invention are defined in general terms by the general formula (ΙΠ). Preferably, R ³ and R ^{4 in} formula (III) are the same groups as preferred substituents for formula (I) according to the invention.

The aldehydes and ketones of formula (III) are well known in the art of organic chemistry.

The orthoesters and orthoic acid amides of formula (IV) are well known in the field of organic chemistry.

In the process (a) of the invention, inert organic solvents may be used as diluents. These include in particular: aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers such as diethyl ether, dioxane, tetrahydrofuran and dimethyl or dictyl ether of ethylene glycol; nitriles such as acclonitrile and propionitrile; esters such as ethyl acetate; and sulfoxides such as dimethyl sulfoxide.

Process (a) of the present invention is preferably carried out in the presence of a suitable reaction-promoting material. Examples of such excipients are: certain acids such as sulfur-21

Acid and the hydrochloride, bases such as sodium, potassium hydroxide and triethylamine; and water retention agents, such as sodium sulfate and molecular sieves.

The water released during the reaction can also be removed from the reaction mixture by azeotropic distillation.

In carrying out process (a) of the invention, the reaction temperature may be varied over a relatively wide range; in general, at temperatures between -20 'C and 150' C, preferably between 0 'C and 120' C.

In carrying out the process (a) of the present invention, 1 mol of the 5-amino-1-arylpyrazole derivative (Π) is generally reacted with 1.0 to 10.0 mol, preferably 1.05.0 mol, of the aldehyde or ketone (ΠΙ). , optionally in the presence of 0.01 to 5.0 moles, preferably 0.1 to 1.5 moles, of a reaction aid (excipient).

The reaction is carried out, the reaction mixture is worked up and the reaction products are isolated by methods well known in the art.

In carrying out process b) of the invention, inert organic solvents may be used. These include in particular: aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons such as gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; and ethers such as diethyl ether, dioxane, tetrahydrofuran and dimethyl or diethyl ether of ethylene glycol; nitriles such as acetonitrile and propionitrile; and alcohols such as methanol, ethanol and propapanol.

However, it is also possible to use an excess of orthoester or orthoic acid amide (IV) in the reaction in such a way that it also serves as a solvent.

Process b) according to the invention is optionally carried out in the presence of a suitable reaction aid (excipient). Such substances are in particular organic or inorganic acids such as hydrochloric acid, acetic acid or p-toluenesulfonic acid. However, process b) according to the invention can be carried out without such an excipient.

In process b) of the invention, the reaction temperature can be varied within a relatively wide range. Generally, temperatures of -20 to 150'C, preferably 0 to 100'C, are employed.

In carrying out the process (b) according to the invention, generally 1.0-20.0 moles, preferably 1.0-10.0 moles of orthoester (TV) are used per mole of 5-amino-1-arylpyrazole (H). or orthoic acid amide and optionally 0.0110.0 mol, preferably 0.1-1.5 mol, of the reaction aid.

The reaction, processing of the reaction mixture and isolation of the reaction products are carried out according to generally known methods.

The active ingredients are well tolerated by plants and have low toxicity to warm-blooded animals. Therefore, the compounds can be used in agriculture, forests, for the protection of stockpiles and structural materials for the control of animal pests, in particular insects, arachnids and nematodes. The active ingredients are both normal and resistant strains and are effective against all or some of their developmental stages

From the order of the Isopods, for example, Oniscus asellus, Annadillidum vulgare, Porcellio scaber.

From the order of the Diplopods, for example, Blaniulus guttulatus.

From the order of the Chilopods, for example, Geophilus carpophagus, Scu t igera spp.

From the order of the Symphylaxis, for example, Scutigerella immaculata.

From the order of the Thysanuras, for example, Lepisma saccharina. 15 From the order of the Collembolas, for example, Onychiurus armatus.

From the order of Orthopteras, for example, Blatta orientalis,

Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp.,

Locusta migrratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

For example, from the order of the Dermaphores, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of Anoplura, for example, Phylloxera vastatrix, Pemphígus spp., Pediculus humanus corporis, Haematopinus spp., Linognatus spp.

For example, from the order of the Mallophagus, Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoral, Thrips tabaci.

From the order of heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doraiis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosip. , Euscelis bilobarus, Nephotettix cincti., Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla SPP45 of the order Lepodiptera, e.g. , Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurbe50 reilla, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heiothis spp., Laphygma exigua, Mamestra brassicae, Prolis flammea, Panolis flammea. ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Catcher nubila5 5 lis, Ephestiella kuehn., Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleopteras, for example, Anobium puncta60 needle, Rhizopertha dominica, Bruchidius abtectus,

HU 203 645 Β

Acanthscelides obtectus, Hylotrupes ba julus, Agelastica alni, Laptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oiyzaephilus surinamensis, Anthonomus spp. Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Melighetes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoder. , Melolontha melolontha, Amphimallonsolstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocama spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomia spp., Cuterebra spp., Gastrophilus spp., Hyppobca. Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oxcinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonapters, for example, Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnids, for example, Scorpio maurus, Latrodectus mactans.

From the order of the Acarines, for example, Acarus siro, Argas spp., Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp. ., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The active compounds of the invention are not only plant, health and stock. they are effective against pests, but can also be used in veterinary practice against animal parasites (ectoparasites) such as shields, skin mites, ticks, running mites, flies (stinging and sucking flies), parasitic fly larvae, lice, chewing needles, feathers and fleas

The active compounds of the present invention are effective against both normal and resistant species and strains and at all stages of parasitic and non-parasitic development of ectoparasites.

The active compounds according to the invention are distinguished by their very strong insecticidal activity. They are therefore useful in controlling insect pests such as horseradish beetle (Phaedon cochleariae), 'green apricot aphid (Myzus persícac) or bean black aphid (Aphis fabae). In doing so, the active compounds of the invention not only provide a protective effect, but also have a systemic effect when absorbed on the leaf or root.

In addition, the active compounds of the present invention are useful in controlling soil-borne insects, for example, they can be successfully used in controlling soil maggots (Phorbia antiqua) in the soil.

Furthermore, the active compounds according to the invention have a very strong effect on the health and storage stock! against pests, so they can be successfully used, for example, to control the bug beetle (Blattella germanica).

The active compounds of the present invention are particularly useful in controlling warm-blooded parasites such as Boophilus microplus.

The active compounds are formulated into conventional formulations such as solutions, emulsions, soluble powders, suspensions, powders, dusts, foams, pastes, granules, aerosol formulations, suspensions and emulsifiers. They can be impregnated with natural and synthetic materials, microcapsules can be used to form polymeric materials and seed coatings, and formulations of the active ingredients with flammable fillers, such as fume cartridges, cans and spirals, and the ULV process can be misted or cooled.

The compositions may be prepared in a manner known per se, for example, by mixing the active compounds with carriers, i.e. liquid solvents, pressurized liquid gases and / or solid carriers, optionally with surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. substances may also be added. When water is used as a carrier, organic solvents may also be used as co-solvents. Suitable liquid solvents are essentially aromatic compounds such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexanes or paraffins, alcohols, glycol as well as their esters and ethers, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide, dimethyl sulfoxide and water. Liquid gaseous carriers are understood to include materials such as aerosol propellants such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide. Solid carriers include natural rock flour such as kaolin, clay earth, talc, chalk, quartz, attapulgite, mintmorillonite or diatomaceous earth, and synthetic rock flour such as highly dispersed silica, alumina and silicates. Solid carriers for granules include granules made from crushed and fractionated natural rocks such as chelate, marble, pumice, sepiolite, dolomite, inorganic and organic flours, and granules made from organic materials such as sawdust, coconut shells, corn cobs and tobacco stalks. Emulsifiers and / or foaming agents include n-ionic and anionic emulsifiers such as polyoxyethylene fatty acid ethers, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol cholether, alkylsulfonates, alkylsulfals,

203645 Β arylsulfonates and protein hydrolysates and lignin, sulphite impurities and

Compositions of the present invention include adhesion promoters such as carboxymethylcellulose, natural and synthetic, powdered, particulate or latex-like polymers such as acacia, polyvinyl alcohol, polyvinyl acetate and natural phospholipids such as cephalin. or lecithin and synthetic phospholipids. Other additives include mineral and vegetable oils

The compositions of the invention also include coloring agents such as inorganic pigments, such as iron oxide, titanium oxide, ferrocyan, and organic dyes such as alizarin, azo and metal phthalocyanine dyes, as well as printing materials such as iron, manganese, boron, they may contain copper, cobalt, molybdenum and zinc salts.

The compositions generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active ingredient

The active compounds of the present invention may be formulated in commercial formulations and in formulations prepared from such formulations with other active substances such as insecticides, insecticides, insecticides, acaricides, nematocides, fungicides, herbicides or herbicides. Suitable insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylurea derivatives and microorganisms.

The active compounds of the invention may also be used in commercial formulations or in combination with adjuvants in the form of application (formulations) prepared from such formulations. Enhancers are compounds that enhance the effects of the active ingredients, although the substance itself may not be effective.

The active ingredient content of the commercially available formulations can be varied within wide limits: the active compound concentration of the formulations may be from 0.0000001% to 95% by weight, preferably from 0.0001 to 1% by weight.

The application (application) is carried out in a manner appropriate to the application forms.

When used against insect pests in health and storage applications, the active compounds of the present invention are extremely durable in wood and clay and exhibit good stability against alkali in lime-containing coatings.

The active compounds of the invention are also useful for controlling insects, mites and ticks in animal husbandry and animal husbandry; consequently, better results can be achieved in animal husbandry and breeding, such as higher milk yields, greater body weight, nicer hair, and longer life.

In this field, the active compounds of the present invention may be administered by conventional means, for example, by oral administration, in the form of tablets, capsules, ingots, granules, or on the skin, or in any other external form. Exterior applications include, for example, dipping, spraying, pouring (powder-on-spot and spot-on), and powder puffs; parenterally, for example by injection, and by the "feed-through" process. They can also be placed on shaped bodies (such as collars, ear tags).

The present invention is illustrated in detail by the following non-limiting examples of preparation and use

Preparation Examples 15 Example 1

Preparation of 5- (benzylideneimino) -1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (dichlorofluoromethylthio) pyrazole (compound of formula I) [ example of process (a)]

8.6 g (0.02 mol) of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (dichlorofluoromethylthio) pyrazole were prepared in 200 ml of anhydrous toluene. The solution was refluxed with a water separator and then 4 drops of concentrated sulfuric acid were added and the mixture was stirred for 2 hours.

6.4 g (0.06 mol) of freshly distilled benzaldehyde are added dropwise. After the addition, the reaction mixture was heated under reflux for an additional 16 hours, and the resulting water was removed with a water separator. After cooling, the reaction mixture was washed three times with 100 ml of saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was chromatographed on a silica gel (silica gel) column using petroleum ether / ethyl acetate 9: 1 as eluent. 8 g (77%) of the title compound are obtained.

Op.:75°C.

Example 2

5- (But-2-en-1-ylidenemino) -1- [2,6-dichloro-4- (tr 140-fluoromethyl) phenyl] -4- (trifluoromethylthio) pyrazole [Preparation of compound of formula (2)] [Example of process (a)]

7.9 g (0.02 mol) of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (trifluoromethylthio) pyrazole, 2.2 g (0 (05 moles) of acetaldehyde, 0.1 g of p-toluenesulfonic acid and 5 g of BAYLITH TE 144 molecular sieve in 100 ml of toluene are stirred for 48 hours at room temperature, filtered, the filtrate is concentrated in vacuo and the residue is chromatographed on a silica gel column. Elution with petroleum ether / ethyl acetate gave 2.5 g (28%) of the title compound as an oil.

1 H-NMR (CDCl ₃ , δ ppm): 1.95 (d, 3H), 7.9 (s, 1H). MS: m / e = 447; 449 (M ⁺ )

Example 3 1- [2,6-Dichloro-4- (trifluoromethyl) phenyl] -4- (dichlorofluoromethylthio) -5- (N, N-dimethylaminomethylidenemino) pyrazole [( Preparation of Compound 3] [Example b)

EN 203 645 Β g (0.025 mol) of 5-amino-1- [2,6-dichloro-4-trifluoromethyl) phenyl] -4- (dichlorofluoromethylthio) pyrazole and 25 ml (0.23 mole) of dimethylformamide-dimethylacetal was refluxed for 12 hours, then concentrated in vacuo, the residue was stirred with water, the product was filtered off with suction and dried. 11 g (97%) of the title compound are obtained.

108 DEG C. (with decomposition).

Example 4 1- [2,6-Dichloro-4- (trifluoromethyl) phenyl] -4- (dichlorofluoromethylthio) -5- (methoxymethylidenedimino) pyrazole [Compound 4] ] [Example of process (b)]

13.0 g (0.03 mol) of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (dichlorofluoromethylthio) pyrazole and 40 ml To the mixture of trimethyl ester of ortho-formic acid (0.39 mole) was added 0.5 g of p-toluenesulfonic acid and the mixture was heated at reflux for 4 hours while distilling off the methanol released on the reaction via a 10 cm Vigreux stopper. For work-up, the reaction mixture is concentrated in vacuo, the residue is dissolved in ligroin, filtered over silica and the solvent removed in vacuo. 11.5 g (81%) of the title compound are obtained in the form of an oil.

1 H-NMR (CDCl ₃ , δ ppm): 3.66 (s, 3H), 7.69 (s, 2H), 7.87 (s, 1H); 8.42 (s, 1H).

Accordingly, the following 1-arylpyrazole derivatives of formula (I) were prepared using the general description provided.

Preparation of compounds of formula (I)

Example number R ¹ -S (O) _n -R ² U 3 ^C X Price Physical data 5 H -SCC1 ₂ F -CH-N (CH ₃ ) ₂ 4- (trifluoromethyl) phenyl op. 77-78'C 6 H -scci ₂ f = ch-oc ₂ h ₅ 2,4-dibromo-6- (trifluoromethyl methoxyphenyl) op.92'C 7 H -scf ₃ benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl op.85'C 8 H -scf ₃ --CH OCjHj 2,6-dichloro-4- (trifluoromethyl ) phenyl ¹ H-NMR *) 7.9; 8.35 9 H -scci ₂ f 4-chloro-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl op.95'C 10 H -scci ₂ f 3-Cl benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl op.91'C 11 H -scci ₂ f 2-Cl benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl op.:105°C 12 ch ₃ -scf ₃ benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl ¹H NMR *) 9.05 13 H 0 II -5-SCCl ₂ F benzylidene 2,6-dichlorophenyl-4- (trifluoro ) phenyl op.:110°C 14 H -so ₂ -cci ₂ f benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 159'C 15 H -so ₂ -cf ₃ benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 132'C 16 H 0 II -s-cf ₃ benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 141 'C 17 H 0 II -s-cf ₃ 4-chloro-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 118 ° C

HU 203 645 Β

Example number R ¹ -S (O) _n -R ² ®mR ⁴ Price Physical data 18 ch ₃ -scf ₃ -CH-OC ₂ H ₅ 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 39-41'C 19 ch ₃ -scq ₂ f -ch-oc ₂ h ₅ 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 76-77 ° C 20 ch ₃ -SO ₂ -CC _{1 2} F -ch-oc ₂ h ₅ 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 111-112'C 21 ch ₃ 0 II -S-CF ₃ -CH-O-C ^ Hj 2,6-dichloro-4- (trifluoromethyl ) phenyl 20 ⁿ D 1.5162 22 ch ₃ —SO ₂ CF ₃ -CH-O-C ^ Hj 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 67-68'C 23 ch ₃ -scf ₃ / CH ₃ -c ^X OCH ₃ 2,6-dichloro-4- (trifluoromethyl ) phenyl „20 ⁿ D 1,5069 24 ch ₃ -SCF ₃ / ¾¾ -C 2,6-dichloro-4- (trifluoromethyl ) phenyl 20 ⁿ D 1.5064 25 ch ₃ -SCF ₃ = ch-och ₃ 2,6-dichloro-4- (trifluoromethyl ) phenyl op. 80-81'C 26 ch ₃ -scf ₃ / CH ₃ ” ^c \ OC ₂ H ₅ 2,6-dichloro-4- (trifluoromethyl methyl) phenyl “20 ⁿ D 1,520 27 H 0 II -s-cf ₃ 3-chloro-benzylidene 2,6-dichloro-4- (trifluoromethyl methyl) phenyl op. 108'C 28 H 0 II -S-CC1 ₂ F 3-chloro-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 110 29 ch ₃ -scci ₂ f benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 127 30 ch ₃ -scf ₃ 4-chlorobenzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 104 31 ch ₃ -scci ₂ f 4-chloro-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 125 32 ch ₃ -scf ₃ 4-methoxy-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 130-135 33 ch ₃ -scci ₂ f 4-methoxy-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 97-99 34 ch ₃ -scf ₃ -4-methyl-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 120-123 35 ch ₃ -scci ₂ f 4-methylbenzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 122-125 36 ch ₃ -scf ₃ 3,4-dichloro-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 94 37 ch ₃ -scci ₂ f 3,4-dichloro-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 91

HU 203 645 Β

Example number R ¹ -S (O) _n -R ² - < ^{R J} (X) _m -R ⁴ Price Physical data 38 ch ₃ -scf ₃ 3-chloro-benzylidene 2,6-dichloro-4- (trifluoromethyl methyl) phenyl 110-112 39 ch ₃ -scci ₂ f 3-chloro-benzylidene 2,6-dichloro-4- (trifluoromethyl ) phenyl 59-62 40 ch ₃ -scf ₃ benzylidene 2-fluoro-6-chloro-4- (tri- fluoro-methyl) phenyl 83-84 41 ch ₃ 0 II -s-cf ₃ benzylidene 2-fluoro-6-chloro-4- (tri- fluoromethyl) phenyl 89-90 42 H -scci ₂ f benzylidene 2-fluoro-6-chloro-4- (tri- fluoromethyl) phenyl 103-109 43 H 0 II -s-cci ₂ f benzylidene 2-fluoro-6-chloro-4- (tri- fluoromethyl) phenyl 88-94 44 H -so ₂ -cci ₂ f benzylidene 2-fluoro-6-chloro-4- (tri- fluoromethyl) phenyl 116-122

*) 1 H-NMR spectra were recorded in deuterochloroform (CDCl 3) using tetramethylsilane (TMS) as internal standard and data were reported in δ ppm chemical shift.

Application examples

In the following application examples, for comparative purposes, 1- (2,6-dichloro-4- (trifluoromethyl) phenyl) -4- (dichlorofluoromethylthio) -5- (N- methylamino) pyrazole and 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- (N-methylamino) -4- (trifluoromethyl) -B thio) -pyrazole was used. 35 (Both compounds are disclosed in European Patent Application Publication No. 0201852).

Testing on Phaedon larvae 40

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a convenient formulation of the active ingredient, 1 part by weight of the active ingredient is admixed with the indicated amount of solvent and emulsifier, and the resulting concentrate is diluted with water to the desired concentration.

The cabbage leaves (leaves of Brassica olearea) are dipped in the desired concentration of active ingredient and then infected with the larvae of Phaedon cochleariae (still wet).

days later, the effect of killing is determined as a percentage: 100% means that all beetle larvae are killed, 0% means that 55 larvae are not killed.

For example, the compound of Example 10 was shown to have a more favorable effect in this assay compared to the state of the art (see table).

The table

agent Concentration % Death rate (%) (A) is known 0.0001 0.00001 100 10 (B) known 0.0001 100 0.00001 0 Example 10 0.0001 100 0.00001 90

Example "B"

Aphis test (systemic test)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a convenient formulation of the active ingredient, 1 part by weight of the active ingredient is admixed with the above amount of solvent and the above amount of coagulant and the resulting concentrate is diluted with water to the desired concentration.

Bean plants heavily infected with black aphid (Aphis fabae) of the bean plant (Vicia faba) are watered individually with 20 ml of the desired concentration of the active ingredient so that the active ingredient does not penetrate the soil but does not wet the stem of the plant. The roots of the plant take up the active ingredient and transfer it to the stem.

After the desired time has elapsed, the effect of the eradication is determined as a percentage: 100% means

20 that all aphids have been destroyed; 0% means that no aphids have died.

For example, the compounds of Examples 2 and 8 were shown to have a more favorable effect in this assay than the prior art. 5

Table B)

agent KonÖentráció % Death rate (%) After 4 days (A) is known 0.1 0 (B) known 0.1 0.01 95 0 Example 8 0.1 0.01 100 100 Example 2 0.1 0.01 100 50

Example "C"

Limit test on soil insects

Insect to be tested: Phorbia antiqua-corn (on soil)

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a convenient formulation of the active ingredient, 1 part by weight of the active ingredient is admixed with the amount of solvent and emulsifier specified above and the resulting concentrate is diluted with water to the desired concentration.

The active ingredient formulation is mixed intimately with the soil. The concentration of the active ingredient in the formulation 35 is practically irrelevant in this respect, but the weight per unit volume of the active ingredient in ppm (-mg / l) is decisive. The soil thus obtained is filled into pots and allowed to stand at room temperature.

After 1 hour, the test pest is introduced into the treated soil and after a further 2 to 7 days, the efficacy of the active ingredient is evaluated by determining the percentage of dead and live insects. The efficacy is 100% if all test pests are killed; and 0% if the same number of test insects survive as in untreated controls.

In this test, for example, the compound prepared in Example 1 showed a more favorable effect than the state of the art.

Table C)

agent Death rate (%) at 1.25 ppm (A) is known 0 Example 1 100

“Example D

Limit Concentration Study by Root-Systemic Effect.

Test insect larvae of Phaedon cochleariae Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a convenient formulation of the active ingredient, 1 part by weight of the active ingredient is admixed with the above amount of solvent, the indicated amount of emulsifier is added and the resulting concentrate is diluted with water to the desired concentration.

The active compound formulation is intimately mixed with the soil. The concentration of the active ingredient in the formulation is practically irrelevant in this regard, but the weight per unit volume of the active ingredient in ppm (-mg / l) is decisive. The soil so treated is placed in pots and planted with cabbage seedlings (Brassica oleracea). The active ingredient is absorbed by the roots of the plant and transferred to the leaves.

After 7 days, only the leaves are infected with the test larvae to detect the root systemic effect (more specifically the systemic effect of the substance absorbed through the root). After another 2 days, evaluation is performed by counting or estimating the number of dead larvae. The number of dead larvae is deduced from the root systemic effect of the drug. This effect is 100% if all test pests are killed and 0% if the same test pests survive as in untreated controls.

For example, the compounds of Examples 2, 7 and 8 showed a more favorable effect in the present invention compared to the present state of the art.

Table D)

agent Death rate (%) at 10 ppm drug concentration (A) is known 0 Example 7 100 Example 8 100 Example 2 '100

Example "E"

Limit Concentration Study by Root-Systemic Effect

Test pest: Myzus persicae Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a convenient formulation of the active ingredient, 1 part by weight of the active ingredient is admixed with the above amount of solvent, the indicated amount of emulsifier is added and the resulting concentrate is diluted with water to the desired concentration.

-9HU 203645 Β

The active compound formulation is thoroughly mixed with the soil. The concentration of the active ingredient in the formulation is practically irrelevant in this respect, but the weight per unit volume of the active ingredient in ppm (= mg / l) is decisive. The soil so treated is placed in pots and the cabbage seedlings (Brassica oleracea) are planted. The active ingredient is absorbed by the roots of the plant and transferred to the leaves.

After 7 days, only the leaves are infected with the test pests for root systemic activity. After another 2 days, the evaluation is performed by counting or estimating the dead pests. The number of dead larvae is deduced from the root systemic effect of the drug. This effect is 100% if all test pests are killed and 0% if the same test pests survive as in the untreated control.

In this test, for example, the compound prepared according to Example 8 showed a more favorable effect than the prior art.

Table "E"

Investigation of 25 root systemic effects against Myzus persicae

agent % /% Mortality at 10 ppm drug concentration Compound of Formula A (known) 0 Example 8 Compound 100

Example "F"

Examination of the LD j ₀₀ value

Insect examined: Blattella germanica (spider mite) Number of tested insects: 10 40

Solvent: acetone is dissolved in 100 volumes of solvent and diluted with additional solvent to the desired concentration.

2.5 ml of the drug solution were pipetted into a petri dish and a 9.5 cm diameter filter paper was placed on its bottom. Allow the Petri dish to remain open until the solvent has completely evaporated. The amount of active ingredient per 1 m ² of filter paper depends on the concentration. The number of test insects indicated above is then placed in a Petri dish and covered with a glass lid.

The condition of the test insects is monitored after 3 days and the percent mortality is determined. 100% means that all 55 tested insects have died; 0% means that no test insect has died.

For example, the compound prepared in Example 2 was shown to have a more favorable effect in this assay than the state of the art. 60

Table F)

agent Concentration of active substance in solution (%) Death in% (B) known 0,002 0 (A) is known 0,002 0 Example 2 0,002 100

"G" Example

ABoophilus microplus resistant / OP resistant

Test with Biarra strain Solvent: 23 parts by weight ethylene glycol monomethyl ether part by weight nonylphenol polyglycolol ether

In order to prepare a convenient formulation of the active ingredient, 3 parts by weight of active ingredient are mixed with 7 parts by weight of the above solvent mixture and the resulting concentrate is diluted with water to the desired concentration.

mature Boophilus microplus slit. the pest is immersed in the active compound to be tested for 1 minute, then transferred to a plastic beaker and kept in an air-conditioned room, and the rate of death is determined,

For example, the compound prepared in Example 4 was shown to have a more favorable effect in this assay than the state of the art.

Table G)

agent Active ingredient concentration in ppm Death rate% 10000 50 (A) is known 3000 50 1000 50 300 0 10000 50 3000 50 (B) known 1000 50 300 50 100 50 30 0 10000 100 3000 100 Example 4 1000 100 of 300 100 100 50 30 0

The following examples serve to prepare the compositions of the present invention.

1. Part Dust of Compound The active ingredient of Example 1 is mixed with 95 parts by weight of ground limestone powder and the

GB 203 645 Β Dust is ground to a fine powder The resulting composition is sprayed onto the plants or their surroundings in the required amounts.

2. Wettable powder

a) Formulation of liquid active ingredient One part by weight of the active ingredient of Example 2, dibutylnaphthalene sulfonate, 4 parts by weight of lignin sulfonate, 8 parts by weight of highly dispersed silica and 60 parts by weight of limestone powder is added and the mixture is ground to a powder. Before use, enough water is added to the wettable powder to achieve the desired concentration.

b) Solid active ingredient formulation

To form a wettable powder, 50 parts by weight of the compound of Example 10 are added with 1 part by weight dibutylnaphthalene sulphonate, 4 parts by weight lignin sulphonate, 8 parts by weight of highly dispersed silica and 37 parts by weight of natural rock powder. Before use, sufficient water is added to the wettable powder to achieve the desired concentration in the permeate.

c) Solid active ingredient formulation

90 parts by weight of the compound of Example 7 are mixed with 1 part by weight of dibutylnaphthalene sulphonate, 5 parts by weight of sodium lignin sulphonate, 2 parts by weight of highly dispersed silica and 2 parts by weight of powdered natural rock to make a powder. Before use, sufficient water is added to the wettable powder to achieve the desired drug concentration in the spray.

3. Emulsifiable concentrate

a) Formulation of solid active ingredient The active ingredient of Example 1 was dissolved in a mixture of 55 parts by weight of xylene and 10 parts by weight of cyclohexanone and 10 parts by weight of a mixture of calcium dodecylbenzene sulphonate and nonylphenol polyglycol ether as emulsifier. Before use, sufficient water is added to achieve the desired drug concentration.

b) Liquid active ingredient formulation To 5 parts by weight of the active ingredient of Example 4 was added 5 parts by weight of 67% calcium dodecylbenzene sulfonate in butanol and 5 parts by weight of nonylphenol polyglycol ether. Prior to use, sufficient water is added to the emulsifiable concentrate to achieve the desired drug concentration.

part consists of powdered limestone. The mixture was treated in a mixer until a smooth, bulk, non-dusting granulate was obtained.

4. Granules

(a) Formulation of liquid active ingredient

One part by weight of the active ingredient of Example 2 was sprayed onto 9 parts by weight of granulated absorbent material. The granulate is sprayed onto the plants or their surroundings to be treated.

b) Formulation of solids 2 parts by weight of spindle oil and 7 parts by weight of active compound premix are added to a particle size sand of 0.5-1.0 mm particle size. The premix is 75 parts by weight of the compound of Example 10 and 25 parts by weight.

Claims (2)

PATENT CLAIMS Insecticidal and acaricidal compositions, characterized in that they contain from 0.1 to 95% by weight of the active ingredient of 1-arylpyrazole of the formula I - in the formula I R ¹ is hydrogen or C 1-4 alkyl, R ^{2 is C} 1 -C 4 haloalkyl, R ³ is hydrogen or C 1-4 alkyl, R ⁴ is C 1 -C 4 alkyl or phenyl optionally substituted with halo, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, X is O or -N - (C 1 -C ₄ alkyl) m is 0 or 1 and n is 0.1 or 2 and Ar is phenyl substituted with halogen, C 1-4 haloalkyl, or C 1-4 haloalkoxy, solid supports such as powdered minerals or synthetically produced silica, or liquid solvents such as aromatic compounds, preferably xylene or cyclohexanone; substances, preferably alkylaryl polyglycol ether or sulfonates. 2. A process for the preparation of the arylpyrazoles of formula (I) which are useful as active ingredients in the compositions according to claim 1, wherein R ¹ is hydrogen or C 1-4 alkyl, R ^{2 is C} 1 -C 4 haloalkyl, R ³ is hydrogen or C 1-4 alkyl, R ⁴ is C 1 -C 4 alkyl or phenyl optionally substituted with halo, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, X is O or -N- (C 1 -C ₄ alkyl) m is 0 or 1 and n is 0.1 or 2 and Ar is phenyl substituted with halogen, C 1-4 haloalkyl or C 1-4 haloalkoxy, characterized in that: a) for the preparation of a compound of formula (Ia) wherein R ¹ , R ² , R ³ , R ⁴ , Ar and n are as defined above, a 5-amino-1-arylpyrazole of formula (Π) wherein R ^1, R ^2, Ar and n are as stated above - a (ΙΠ) an aldehyde or ketone of formula - in formula (ΙΠ) R ³ and R ⁴ are as defined above if appropriate in the material in the presence of a diluent and, optionally, obsession -111 HU 203 645 Β b) for the preparation of a 1-arylpyrazole derivative of formula Ib - in formula Ib, X ¹ is oxygen or C 1-4 N-alkyl, while R ¹ , R ² , R ³ , R ⁴ , Ar and n are as defined above - a 5-amino-1-arylpyrazole derivative of the formula (Π) with an orthoester of the general formula IV - in the formula (TV) Alk represents a C 1-4 carbon atom alkyl, while R ³ , R ⁴ and X ¹ are as defined above, optionally in the presence of a diluent and optionally an excipient.